Aldehydes of the cyclohexane series



Patented Aug. 23, 1932 "7 UNITED STATES SIGNORS 'ro WINT 'RQP CHEMICAL *POR-ATION or NEW YORK ANGELO KNORR, or BERLIN, ANDALBERT wEIssENBoRn, or ro'rsnAM', Gamma, As-

ALDEHYDES OF THE CYCLOHEXANE SERIES No Drawing. Application filed June 5, 1930, Serial No. 459,420, and in Germany zr uneiaisaer and its nucleal substitution products have a surprisingly novel odor, which is complete- 1y different from the ionone odor and has an agreeably bitter character, resembling nuts and leaves. This characteristic odor makes these Compounds valuable in produc-.

ing special flower-like efiect-s in floral oils and for building up quite new fancy perfumes.

The aldehydes in question, hitherto unknown, may be made, for example, by condensing a ketone .of fewer carbon atoms with a halogen acetic ester as described in German Patent No. 17427 9 and splitting up the glycidic acid thus obtained as described in German Patent No. 174239.

The following examples serve to illustrate our invention, the parts being by weight.

Example 1.--A mixture of 550 parts of chloroacetic acid ethyl ester and 750 parts of 4 (2.2.G-trimethyl-cyclohexyl) -butanone (2) are added drop by drop during several hours while cooling'intensively to 100 parts of finely subdivided sodium which is covered by benzene or xylene.

The occurring reaction may be explained by the following equation:

OH: OH:

The solvent used and the starting material boils at, a pressure of4-5 mercury at 1' free glycidic acid is separated from the mixture by addition of mineral acid. By heating the glycidic acid under diminished pressure, carbon dioxide evolves and 460 parts of 4 (2.2.6-trimethyl-cyclohexyl) -2-methylbutanal are obtained.

This compound forms a colorless oil boiling at 115120 C. at a'pressure' of 2 3 mm. mercury. It has a nut-like odor. I

Example 2.A mixture of 550 parts ofv chloroacetic acid ethyl ester and 800 of 5(2.2.6 trimethyl cyclohexyl) propanone (3) are added drop by drop during several hours While cooling intensively to 100 parts of finely subdividedsodium covered by benzcne-oxylene. 1

The occurring reaction may be explained by the following equation:

CH3, CH:

\ CHr-OH: o r we From the reaction mixture after remove- COMPANY, me, or rrEw xonxpm x nlooni so ment of the solvent and of the starting material not consumed, the corresponding glynot consumed are removed from the reaction to 186 C. under a pressure of 5 mm. merv mixture. The glycidic acid ester obtained 'cury. The ester issaiponifiedby warming it 109 with an aqueous solution of sodium hydroxide. The glycidic acid is separated from the solution by addition of a mineral acid. The glycidic acid is heated in a vacuum, carbon dioxide evolves and 350.parts of 4(2. 2 .6.-trimethylrcy'clohexyl) -2-ethylbutanal'. are 3 obtainedv forming a colorless oil, boiling at a pressure of'3-4L mm. mer- 125-130 C. at w y: '7 v Our invention is not limited to'the'foregoing examples 'or tothe specific details given therein.

Other alkyl derivatives of the general f rmula imeutionedabove are obtainable in an analogous manner when starting from a corresponding cyclohexy'l-butanone. The

finely subdivided sodium used in theforegoing examples maybe substituted by another alkaline condensing agentsuch as sodium g8) amide or sodium ethylate.

From our new compounds perfumes may be prepared according to the fo'llowingexamples:

. Example 3. Basis for fancylperfame 20 parts of .4(2.2.6-trimethyl-cyclohexyl)- Q-methyl-butanal 5 parts of ionone V e 10 parts of methylionone Biparts of ylang-ylang oil 1 5 partsof artificial jasmine oil 7 4 partsof heliotropine .8 parts of cumarin 5 ,10 parts of phenyl-ethyl alcohol 15 parts of bergamot oil 5 parts of orangeoil 5 parts of East Indian sandal wood oil 5 parts of ambrette musk 100.1)i1rts. Example 4. Basis for a floral oil WW i H R--CH:CH2(kHC/H=. O, so

or LIB-methylated cyclohexyl radical, these 7 compounds being at; room temperature in the pure state colorlessoils ofanlagreeable bit- .95 iter odor resembling nuts and leaves. K

wherein R stands for a cyclohexane nucleus '2. As new products the compounds of the general formula V X X /O\ V allgyl' V 1120 onon -oinonon=o,-

Hi0 EX wherein Xstands for hydrogen or methyl, these compounds being atroom temperature 1n ;the pure state colorless oils of an agreeable bitter odorresembling nuts and leaves.

3. 'As new products the compounds of the general formula on on;

/C\ alkyl H1O oHoH2'oH2bH-o11=o,' 8r 0 H2 HCH3 I Hz I these compounds being at room temperature 1n the pure state colorless oils of a nut-like so odor.

4. As a new product 4(2.2.6-tri1nethylcyclohexyl) -2-methyl-butanal corresponding to the formula 7 CH3 CH3 I p /'C'\ 1 1 7 7 H20 'CHOHzCH2OH-OH=O H2 on on,

being a colorless .oil boiling atv -120? G. at a .pressure'of 2 3 nnnomercury and hav ing a nut-like odor. i

I As a new product, l-(2.2.6-trimethyl- 3.05 cyclohexyl).-2-ethyl'-butanal corresponding to the formula: p f 7' being acolorlessoil, boiling 125,155 1 0 -1 V Caa't a pressureof 3 to. 4 mm. mercury.

In testimony whereof we our signa tu e DR. ALBERT WEISSENBORN. 12 

